EP1798794B1 - Ensemble d'électrode à membrane pour pile à combustible polymère solide et pile à combustible polymère solide - Google Patents

Ensemble d'électrode à membrane pour pile à combustible polymère solide et pile à combustible polymère solide Download PDF

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Publication number
EP1798794B1
EP1798794B1 EP05775096A EP05775096A EP1798794B1 EP 1798794 B1 EP1798794 B1 EP 1798794B1 EP 05775096 A EP05775096 A EP 05775096A EP 05775096 A EP05775096 A EP 05775096A EP 1798794 B1 EP1798794 B1 EP 1798794B1
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Prior art keywords
region
membrane
polymer electrolyte
electrolyte membrane
electrode assembly
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EP05775096A
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German (de)
English (en)
Japanese (ja)
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EP1798794A4 (fr
EP1798794A1 (fr
Inventor
Tetsuji Shimohira
Shinji Kinoshita
Hirokazu Wakabayashi
Ichiro Terada
Yoshihiro c/o Matsushita Electric Industrial Co. Ltd Intellectual Property Rights HORI
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Panasonic Corp
AGC Inc
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Asahi Glass Co Ltd
Panasonic Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a membrane-electrode assembly for polymer electrolyte fuel cells, and a polymer electrolyte fuel cell. Particularly, it relates to a membrane-electrode assembly for polymer electrolyte fuel cells, and a polymer electrolyte fuel cell having excellent dimensional stability and mechanical strength, and having high durability at the time of power generation.
  • Fuel cells are expected to be widely used in the future since their power generation efficiency is high, and their load to the environment is light.
  • Particularly polymer electrolyte fuel cells are expected to be widely used for movable bodies such as automobiles, or as distributed power generation system, or cogeneration systems for home use, since their power density is high and their operating temperature is low, whereby downsizing can be carried out.
  • FIG. 17 A cross-sectional view of a single cell for conventional fuel cells is shown in Fig. 17 .
  • a single cell 1 for fuel cells has a polymer electrolyte membrane 11.
  • This polymer electrolyte membrane 11 usually has a thickness of from about 20 to 120 ⁇ m, and a cation exchange membrane made of a perfluorocarbon polymer having chemically stable sulfonic groups is used for it.
  • two catalyst layers 27 and 28 each containing a metal catalyst are bonded to both outer surfaces 11a of the polymer electrolyte membrane 11. These catalyst layers 27 and 28 are formed on the center portion of the polymer electrolyte membrane 11, and a portion not bonded to the catalyst layers 27 and 28 is left along its periphery.
  • a membrane-catalyst layer assembly 31 is constituted by such a polymer electrolyte membrane 11 and catalyst layers 27 and 28, and gas diffusion layers 33 and 34 are respectively disposed on both outer surfaces 31a of the membrane-catalyst layer assembly 31 on the side of the catalyst layers 27 and 28.
  • these gas diffusion layers 33 and 34 have sizes which are the same as or larger than the sizes of the catalyst layers 27 and 28, and they are formed from e.g. carbon paper or carbon cloth.
  • the gas diffusion layers 33 and 34 may be disposed to cover not only the surfaces of such catalyst layers 27 and 28 but also their sides. In such a case, the gas diffusion layers 33 and 34 may also be contacted with the polymer electrolyte membrane 11 at contact surfaces 33a.
  • a membrane-electrode assembly 37 is constituted by the membrane-catalyst layer assembly 31 and the gas diffusion layers 33 and 34, and, on both outer surfaces 37a of the membrane-electrode assembly 37, on the side of the gas diffusion layers 33 and 34, gas channels 47 and 48 are formed between them and separators 41 and 42.
  • the separators 41 and 42 have such sizes as to cover the entire surface of the polymer electrolyte membrane 11, and concave grooves 45 and 46 are engraved at the respective portions facing the catalyst layers 27 and 28, so that when the separators 41 and 42 and the membrane-electrode assembly 37 are fastened, such grooves 45 and 46 will form the gas channels 47 and 48.
  • gaskets 53 and 54 are located for sealing so that a fuel gas and an oxidant gas will not leak to outside, and when the separators 41 and 42 and the membrane-electrode assembly 37 are assembled, such gaskets are interposed between the separators 41 and 42 and the polymer electrolyte membrane 11, so that the gas channels 47 and 48 are sealed against outside.
  • a single cell 1 is constructed as a minimum unit for power generation by a fuel cell, and in a case of using such single cells 1 for fuel cells, a plurality of single cells 1 may be used as laminated or stacked so as to generate a practical voltage.
  • a membrane not substantially containing a reinforcing material in the vicinity of the center of the conductive portion of the polymer electrolyte membrane and containing a reinforcing material such as fiber, fabric, fibril or porous membrane in the vicinity of the boundary between the conductive portion and the non-conductive portion around it has been proposed (see Patent Documents 3 and 4).
  • this membrane in the vicinity of the center, its strength is insufficient though resistance is low, and the gas permeability of the reinforced portions is suppressed but the suppression is still insufficient, and during a long-term operation, a defect of the membrane or short circuiting was likely to occur in the vicinity of the end portions of the electrode catalyst layers.
  • a membrane-electrode assembly which is prepared in such a manner that holes of 3 mm ⁇ are formed in 7 rows ⁇ 7 columns on a polytetrafluoroethylene (PTFE) film so that the distance between the centers of adjacent holes is 6 mm, a perfluorosulfonic acid polymer is impregnated in the holes and dried to prepare a membrane having a conductive portion with an area of 39 mm ⁇ 39 mm, and then electrodes of 50 mm ⁇ 50 mm are bonded on both sides of the membrane (see Patent Document 5).
  • PTFE polytetrafluoroethylene
  • a polymer electrolyte membrane having such a structure that portions of the contact surfaces 33a are reinforced, is considered to be preferred.
  • a membrane-electrode assembly which is prepared in such a manner that a sealing material of tetrafluoroethylene/propylene copolymer is applied on peripheral portions of the gas diffusion layers and dried to prepare assistant gaskets having a width of from 2 to 10 mm and a thickness of 60 ⁇ m, and catalyst layers are formed inside of such gaskets and then bonded with an ion exchange membrane (see Patent Document 6).
  • a membrane-electrode assembly which is prepared in such a manner that on center portions of gas diffusion layers, catalyst layers with a smaller area are respectively applied and dried, followed by bonding with an ion exchange membrane having fluororesin sheets with an opening of the same size as the catalyst layers bonded thereto (see Patent Document 7).
  • misalignment may occur at the time of bonding the above gas diffusion layers with the ion exchange membrane, and the catalyst layers and the fluororesin sheets may overlap to form defects.
  • a membrane-electrode assembly which is prepared in such a manner that a fluororesin sheet having an opening with a certain size is bonded on each side of an ion exchange membrane, a catalyst layer with the same size as the opening is applied to the opening and dried, and then a gas diffusion layer larger than the opening is bonded to the catalyst layer (see Patent Document 8).
  • a polymer electrolyte membrane is considered to be preferred, which has such a structure that the vicinity of the inner portions 30 of the gaskets 53 and 54 is reinforced.
  • a membrane-electrode assembly which has such a structure that reinforcing frames of a polymer sheet are interposed between gaskets and a polymer electrolyte membrane (see Patent Document 2).
  • the present invention has been made under such conventional problems, and it is an object of the present invention to provide a membrane-electrode assembly for polymer electrolyte fuel cells and a polymer electrolyte fuel cell having excellent dimensional stability and mechanical strength, and having high durability at the time of power generation.
  • the present invention is to achieve the above object, and has the following gists.
  • a membrane-electrode assembly for polymer electrolyte fuel cells which comprises a polymer electrolyte membrane, and electrodes comprising catalyst layers containing a catalyst, disposed on both sides of the polymer electrolyte membrane, and gas diffusion layers supporting the catalyst layers inside of their peripheral portions, characterized in that the polymer electrolyte membrane has a first region having proton conductivity over the entirety in the thickness direction of the membrane and a second region, located at the outer peripheral portion of the first region and having a non-perforated sheet disposed so that the second region has no proton conductivity over the entirety in the thickness direction of the membrane, and outer edges of the catalyst layers are disposed so as to be located in the second region, wherein a partition line for partitioning the first region and the second region is virtually defined, and the distance between the partition line and the catalyst layer end edge is from 1 to 12 mm, wherein the polymer electrolyte membrane has a third region having proton conductivity in a further outer peripheral portion of the second region, and wherein the polymer electroly
  • the outer edges of the catalyst layers are disposed so as to be located in the second region, so that the increase of gas leakage is suppressed even when the pressure is strongly exerted on the ends of the electrode catalyst layers during bonding of the electrodes or even when the polymer electrolyte membrane is partly damaged by creeping during the operation, whereby it is possible to prevent deterioration of the polymer electrolyte membrane or short circuiting of the electrode due to e.g. a local burning reaction.
  • a membrane-electrode assembly for fuel cells having a long life.
  • setting of the third region allows also the peripheral portion of the membrane to have proton conductivity. Therefore, for example, in a case where the polymer electrolyte membrane is formed from a perforated sheet and an ion exchange resin, it is possible to prevent peeling of the perforated sheet and the ion exchange resin.
  • the proton conductivities in the first and third regions are not particularly limited so long as they are in such a range that the effect of the present invention can be obtained, and the range is practically from about 0.01 to about 0.5 S/cm.
  • the proton conductivity in the second region is at most 0.001 S/cm which is sufficiently lower than those of the first and third regions.
  • the polymer electrolyte membrane which constitutes the membrane-electrode assembly is further reinforced by the reinforcing material. Further, the proton conductivity is secured by the ion exchange resin filled in the void portions.
  • reinforcement of the first region it is possible to improve the strength of the polymer electrolyte membrane and make it hardly be damaged.
  • Materials of the reinforcing material in the first region and the reinforcing material in the second region may be different, but are preferably the same and further preferably structurally integral.
  • the reinforcing material does not have void portions. Therefore, in a case where the reinforcing material is made of a perforated sheet having through-holes formed, it is possible to use a perforated sheet having through-holes formed in the first region and having no through-holes formed in the second region.
  • the reinforcing material in the first region and a non-perforated sheet in the second region may be prepared separately such that such a reinforcing material is disposed in the first region and a sheet formed with no through-holes is disposed in the second region.
  • the reinforcing material in the first region and the non-perforated sheet may or may not be bonded. If they are not bonded, the reinforcing material in the first region and the non-perforated sheet may be bonded by filling the ion exchange resin.
  • the entire regions of from the outer edges of the catalyst layers to the outer edges of the gas diffusion layers are disposed so as to be located in the second region, so that the increase of gas leakage is suppressed even when the pressure is strongly exerted on the ends of the gas diffusion layers during bonding of the gas diffusion layers or even when the polymer electrolyte membrane is partly damaged by creeping during the operation, whereby it is possible to prevent deterioration of the polymer electrolyte membrane or short circuiting of the electrode caused by e.g. a local burning reaction.
  • a polymer electrolyte membrane-electrode assembly for fuel cells having a long life can be obtained.
  • the inner peripheral portions of the gaskets are disposed so as to be located in the second region so that the increase of gas leakage is suppressed even when the pressure is strongly exerted on the polymer electrolyte membrane during bonding of the gaskets or even when the polymer electrolyte membrane is partly damaged by creeping during the operation, whereby it is possible to prevent deterioration of the polymer electrolyte membrane or short circuiting of the electrode caused by e.g. a local burning reaction.
  • a membrane-electrode assembly for fuel cells having a long life can be obtained.
  • the polymer electrolyte membrane may be made solely of the filled layer having respective void portions filled with the ion exchange resin. However, it is preferred that a layer made solely of the ion exchange resin is formed on at least one side of the filled layer to constitute such a polymer electrolyte membrane, whereby electroconductivity will be increased.
  • the ion exchange resin filled in the void portions may be the same or different from the ion exchange resin of the layer formed on the filled layer.
  • the layer formed on the filled layer is not reinforced by the filled layer, and therefore, as the ion exchange resin constituting such a layer, it may be effective to use a different resin, such as a resin having a strength higher than that of the ion exchange resin filled in the void portions, such as a resin having a low ion exchange capacity.
  • the layer having the void portions filled with the ion exchange resin is reinforced by the filled layer, and therefore, the strength of the ion exchange resin itself may not be so high. Accordingly, an ion exchange resin having a high ion exchange capacity and not having high strength may be used to increase the electroconductivity of the obtainable polymer electrolyte membrane.
  • the polymer electrolyte membrane which constitutes the membrane-electrode assembly of the present invention is reinforced by the perforated sheet.
  • the material for the perforated sheet one having substantially no ion exchange groups is used, but since a plurality of through-holes are present in the first region, and the ion exchange resin is filled therein, the proton conductivity is secured in a humidified atmosphere.
  • the average cross-sectional area per through-hole is preferably from 1 ⁇ 10 -3 to 20 mm 2 .
  • the open area ratio of the perforated sheet is lower than 30%, the resistance of the polymer electrolyte membrane finally obtainable tends to be high. If the open area ratio of the perforated sheet is higher than 80%, the strength of the polymer electrolyte membrane tends to remarkably decrease. Therefore, the open area ratio of the perforated sheet is preferably from 30 to 80%.
  • the material (constituting material) for the perforated sheet is at least one member selected from the group consisting of a polytetrafluoroethylene, a tetrafluoroethylene/hexafluoropropylene copolymer, a tetrafluoroethylene/perfluoroalkoxyethylene copolymer, a tetrafluoroethylene/ethylene copolymer, a polyethylene, a polypropylene, a polyetheramide, a polyetherimide, a polyether ketone, a polyether ether ketone, a polysulfone, a polyether sulfone, a polyphenylene sulfide, a polyphenylene oxide, a polyphosphazene, a polyarylate, a polyimide, a polyamide-imide and a polybenzimidazole.
  • Such a perforated sheet may have poor bonding properties depending upon the material, and is preferably surface-treated to improve its bonding properties with the ion exchange resin.
  • the present invention provides a polymer electrolyte fuel cell, which comprises laminated cells, each having separators disposed on both sides of the membrane-electrode assembly as defined in any one of Claims 1 to 10.
  • the outer edges of the catalyst layers are disposed so as to be located in the second region so that the increase of gas leakage is suppressed even when the pressure is strongly exerted on the ends of electrode catalyst layers during bonding of the electrodes or even when the polymer electrolyte membrane is partly damaged by creep during the operation, whereby it is possible to prevent deterioration of the polymer electrolyte membrane or short circuiting of the electrodes caused by e.g. a local burning reaction.
  • a membrane-electrode assembly for fuel cells having a long life.
  • FIG. 1 A cross-sectional view illustrating a single cell for fuel cells as a basis for the first embodiment of the present invention is shown in Fig. 1 .
  • a plurality of through-holes 117 are formed in a center region 121 (hereinafter referred to as the region 1) of a perforated sheet 113 constituting a single cell 100.
  • a region 2 having no through-holes 117 formed, is provided at the periphery surrounding the region 1.
  • a partition line 118 for partitioning the region 1 and the region 2 is virtually defined.
  • a plan view illustrating such a perforated sheet 113 is shown in Fig. 2 .
  • through-holes 117 are filled with an ion exchange resin to form a filled layer 114.
  • resin layers 125 made of the same ion exchange resin are connected to form a polymer electrolyte membrane 111.
  • the vertically sectional view illustrating such a polymer electrolyte membrane 111 is shown in Fig. 4 .
  • catalyst layers 127 and 128 are respectively bonded on both outer surfaces of the polymer electrolyte membrane 111. Such catalyst layers 127 and 128 are formed in the center portion of the polymer electrolyte membrane 111, and a portion not being bonded with the catalyst layers 127 and 128 is left in its periphery. The outer edges of the catalyst layers 127 and 128 are disposed so as to be located in the region 2.
  • a membrane-catalyst layer assembly 131 is constituted by such a polymer electrolyte membrane 111 and catalyst layers 127 and 128, and gas diffusion layers 133 and 134 are respectively disposed on both outer surfaces of the membrane-catalyst layer assembly on the side of the catalyst layers 127 and 128.
  • gas diffusion layers 133 and 134 In order to collect electrons entering or leaving from the catalyst layers 127 and 128 efficiently, such gas diffusion layers 133 and 134 have sizes which are the same as or larger than the sizes of the catalyst layers 127 and 128.
  • a membrane-electrode assembly 137 is constituted by the membrane-catalyst layer assembly 131 and the gas diffusion layers 133 and 134, and, on both outer surfaces of the membrane-electrode assembly 137 on the side of the gas diffusion layers 133 and 134, gas channels 147 and 148 are formed between them and separators 141 and 142.
  • the separators 141 and 142 have the same sizes as the entire surface of the polymer electrolyte membrane 111, and concave grooves 145 and 146 are engraved at their respective portions facing the catalyst layers 127 and 128.
  • the sizes of the catalyst layers 127 and 128 are usually different in some degree by the process. Accordingly, in fact, misalignment in some degree may occur also at end edges of the catalyst layers 127 and 128 shown in Fig. 1 .
  • the catalyst layer end edge 130 Between the end edge of the catalyst layer 127 and the end edge of the catalyst layer 128, one which is closer to the region 1 is defined as the catalyst layer end edge 130 (in the case of Fig. 1 , the end edge of the catalyst layer 128 is closer to the region 1 than the end edge of the catalyst layer 127, and therefore, the end edge of the catalyst layer 128 is defined as the catalyst layer end edge 130).
  • the catalyst layer end edge 130 is disposed so as to be located in the region 2 where the through-holes 117 are not formed in the perforated sheet 113, so that the increase of gas leakage is suppressed even when the pressure is strongly exerted on the catalyst layer end edge 130 during bonding of the electrode or even when the polymer electrolyte membrane 111 is partly damaged by creeping during the operation, whereby it is possible to prevent deterioration of the polymer electrolyte membrane 111 or short circuiting of the electrodes due to e.g. a local burning reaction.
  • the distance between the partition line 118 and the catalyst layer end edge 130 is from 1 to 12 mm, preferably from about 1 to 6 mm, further preferably from about 2 to 4 mm. If it is less than 1 mm, the gas is likely to bypass the region 2 and permeate through the region 1 so that the effect of suppressing deterioration of the membrane cannot be achieved sufficiently, and if it is more than 12 mm, portions of the catalyst layers which are not used effectively, increase so that the power generation efficiency decreases, such being undesirable.
  • the gas permeability in the region 2 changes depending upon the material and the thickness of a sheet to be used, the thickness of the ion exchange resin layer, and the type of the gas, but is preferably at most 1/2, more preferably at most 1/10, of the gas permeability in the region 1. If the gas permeability in the region 2 is more than 1/2 of the gas permeability in the region 1, the effect of suppressing gas leakage in the region 2 cannot be achieved sufficiently, such being undesirable.
  • the material for the perforated sheet 113 is preferably one which has substantially no ion exchange groups and which has a water content of at most 5% after immersion in hot water at 90°C. If the water content is more than 5%, creep is likely to occur by the pushing pressure during bonding of the catalyst layers 127 and 128 or during operation of the fuel cell, whereby the polymer electrolyte membrane 111 is damaged and gas permeability increases, such being undesirable.
  • the average area per through-hole, of the through-holes 117 of the perforated sheet 113 is preferably from 1 ⁇ 10 -3 to 20 mm 2 , more preferably from about 8 ⁇ 10 -3 to 4 mm 2 , particularly preferably from about 1.5 ⁇ 10 -2 to 1 mm 2 .
  • the average area per through-hole 117 is too small, if it is attempted to maintain the open area ratio within a certain range, the number of the through-holes 117 per unit area is obliged to be so large that the productivity tends to be low or filling of the ion exchange resin tends to be difficult.
  • the polymer electrolyte membrane 111 can be made to have uniform and sufficient strength for practical use, and have high productivity and sufficient ion conductivity.
  • the open area ratio in the center region 121 of the perforated sheet 113 having such through-holes 117 formed is preferably from 30 to 80%, more preferably from 50 to 75%, particularly preferably from 62 to 70%. Because, for example, if the open area ratio is too low, the ion conductivity is likely to be prevented, and on the other hand, if the open area ratio is too high, the polymer electrolyte membrane 111 obtainable cannot sufficiently be reinforced and its strength is likely to be insufficient.
  • the sizes or shapes of the through-holes 117 may all be equal, but holes having two or more sizes or shapes may be present as mixed. Further, the shape of the through-hole 117 is not particularly limited, but if it has corners, its strength as the reinforcement tends to be deteriorated because such corners work as notches. Therefore, such a through-hole 117 preferably has a round shape or a shape having no corners.
  • a method of mechanically perforating a sheet to form the perforated sheet 113, or a method for forming of the perforated sheet 113 by the use of a laser beam may, for example, be mentioned, but it is preferred to employ the method of mechanically perforating it because such a method is excellent in mass productivity.
  • a method of mechanically punching it many through-holes 117 may be formed in a short period of time in such a manner that from a few tens to a few thousands sheets for perforated sheets 113 are laminated and punched by using a punching die which can form from a few hundreds to a few ten thousands through-holes 117 all at once thereto.
  • the thickness of such a perforated sheet 113 is preferably from 3 to 50 ⁇ m, particularly preferably from 5 to 30 ⁇ m, in a case where the polymer electrolyte membrane 111 having such a perforated sheet 113 is employed for polymer electrolyte fuel cells.
  • the polymer electrolyte membrane 111 obtainable may not be reinforced sufficiently and the gas leakage blocking property at the end portions of the catalyst layers in the region 2 may not be secured sufficiently.
  • the polymer electrolyte membrane 111 obtainable also becomes too thick, and the ion conduction resistance will be high, whereby the resistance loss will be high and no sufficient performance may be obtained.
  • the thickness of the perforated sheet 113 is desired to be uniform in order that the polymer electrolyte membrane 111 obtainable can uniformly be reinforced.
  • the through-holes 117 in such a perforated sheet 113 are to be filled with an ion exchange resin, whereby the filled layer 114 is to be formed in the perforated sheet 113.
  • a cation exchange resin made of a perfluorocarbon polymer having sulfonic groups is preferred, but as long as it is a cation exchange resin, it is also possible to use e.g. a cation exchange resin made of a hydrocarbon polymer or a partially fluorinated hydrocarbon polymer.
  • the ion exchange resin may be a single one or a mixture of two or more ion exchange resins.
  • such a filled layer 114 is reinforced by the perforated sheet 113, and therefore, the strength of the filled layer 114 itself may not be so high. Accordingly, as the ion exchange resin constituting the filled layer 114, it is preferred to use an ion exchange resin having a high ion exchange capacity though not having high strength, so as to increase the electroconductivity of the polymer electrolyte membrane 111 obtainable.
  • Methods for filling the ion exchange resin in the perforated sheet 113 are not particularly limited, but may, for example, be a method of hot pressing cast membranes formed by e.g. a cast method from a liquid having an ion exchange resin dispersed (dissolved) in a dispersion medium (solvent) (hereinafter referred to as an ion exchange resin-containing liquid), on both outer surfaces of the perforated sheet 113, a method of applying the ion exchange resin-containing liquid on one or both of outer surfaces of the perforated sheet 113, and a method of impregnating the perforated sheet 113 in the ion exchange resin-containing liquid, followed by drying.
  • a method of hot pressing cast membranes formed by e.g. a cast method from a liquid having an ion exchange resin dispersed (dissolved) in a dispersion medium (solvent) (hereinafter referred to as an ion exchange resin-containing liquid), on both outer surfaces of the perforated sheet 113, a
  • such a perforated sheet 113 may be in a state where the filled layer 114 is formed, or may further have a resin layer 125, which is made solely of an ion exchange resin, formed on at least one side or preferably on both sides of the perforated sheet 113.
  • the material for the ion exchange resin constituting the resin layer 125 may be the same or different from that of the ion exchange resin constituting the filled layer 114. In the case of using a different material, it is possible to increase the strength of the resin layer 125 itself, by using, for example, an ion exchange resin having high strength though it has an ion exchange capacity lower than that of the ion exchange resin constituting the filled layer 114.
  • such resin layers 125 may be formed so as to cover the entire regions on both outer surfaces of the perforated sheet 113 as shown in Fig. 4 .
  • such resin layers 125 may be formed larger than the area of the center region 121 so as to cover the entire center region 121 with the peripheral portion 115 of the perforated sheet 113, which is partly left uncovered.
  • such resin layers 125 may be formed by coating during forming of the filled layer 114 on the perforated sheet 113, or may be formed in such a manner that the resin layer 125 is prepared separately and then bonded on the perforated sheet 113 by e.g. hot pressing. Further, the resin layers 125 may be constituted by both the resin layer 125 formed by coating and the resin layer 125 prepared separately.
  • the ion resin-containing liquid may be applied on the perforated sheet 113 to form the resin layers 125, or layers made of resins may separately be prepared by a cast method, such layers may be disposed on both sides of the perforated sheet 113 and hot-pressed to form the filled layer 114 and the resin layers 125 at the same time. Further, such methods may be repeated or combined to form the resin layers 125.
  • the perforated sheet 113 having the filled layer 114 and the resin layers 125 formed as described above constitutes the polymer electrolyte membrane 111 shown in Fig. 1 .
  • the polymer electrolyte membrane 111 may have a plurality of the perforated sheets 113, and in such a case, perforated sheets 113 respectively made of different polymers may be laminated. Further, in such a case, as between the adjacently perforated sheets 113, the respective sides having no resin layers 125 formed, may be in direct contact or the respective resin layers 125 may be in contact with each other.
  • Figs. 6 to 8 show a mode of a single cell for fuel cells as the first embodiment of the present invention.
  • the perforated sheet 213 of the single cell 200 has a region 3 having a plurality of through-holes 117 formed on a further outer peripheral portion of the region 2.
  • a plan view illustrating the perforated sheet 213 is shown in Fig. 7
  • a view taken in the direction of the arrow B-B in Fig. 6 is shown in Fig. 8 .
  • a partition line 151 for partition between the region 2 and the region 3 is virtually defined.
  • the region 2 is formed in the form of a frame as shown in Fig. 7 .
  • setting of the region 3 allows the ion exchange resins on both surfaces to be connected through the through-holes 117 of the perforated sheet 213 also at the peripheral portion of the membrane, whereby it is possible to prevent peeling of the perforated sheet 213 and the ion exchange resins.
  • the catalyst layer end edge 130 is located at an about center portion of the width of the region 2. Further, such a width of the region 2 is preferably from about 2 to 24 mm, more preferably from about 3 to 12 mm, further preferably from about 4 to 8 mm.
  • the average area per through-hole 117 gradually becomes small towards the region 2 as shown in Fig. 9 .
  • the open area ratio gradually, it is possible to prevent concentration of the stress at the boundary between the region 1 and the region 2 and the boundary between the region 2 and the region 3.
  • the number of the through-holes 117 may gradually be decreased as shown in Fig. 10 .
  • the material (constituting material) for the perforated sheet to be used in the present invention is at least one member selected from the group consisting of a polytetrafluoroethylene, a tetrafluoroethylene/hexafluoropropylene copolymer, a tetrafluoroethylene/perfluoroalkoxyethylene copolymer, a tetrafluoroethylene/ethylene copolymer, a polyethylene, a polypropylene, a polyether amide, a polyether imide, a polyether ketone, a polyether ether ketone, a polysulfone, a polyether sulfone, a polyphenylene sulfide, a polyphenylene oxide, a polyphosphazene, a polyarylate, a polyimide, polyimide amide and a polybenzimidazole.
  • Such a perforated sheet 113 or 213 may have poor bonding properties depending upon the material, and is preferably surface-treated to improve its bonding properties with the ion exchange resin.
  • the method of surface treatment is not particularly limited, but is suitably a chemical etching treatment, corona discharge treatment, plasma surface treatment or the like.
  • FIG. 11 The cross-sectional view illustrating a single cell for fuel cells as a basis for the second embodiment of the present invention is shown in Fig. 11 .
  • a plan view illustrating the perforated sheet 113 is the same as Fig. 2
  • a view taken in the direction of arrow A-A in Fig. 11 is the same as Fig. 3
  • a vertically cross-sectional view illustrating the polymer electrolyte membrane 111 is the same as Fig. 4 , and such views are therefore omitted.
  • the gas diffusion layers 133 and 134 are disposed to cover not only the surfaces of the catalyst layers 127 and 128 but also their sides, and the gas diffusion layers 133 and 134 are in surface contact with the polymer electrolyte membrane 111 at the contact surfaces 133a.
  • the gas diffusion layers 133 and 134 are formed from e.g. carbon paper or carbon cloth. Further, such gas diffusion layers are disposed so that the regions of from outer edges of the catalyst layers 127 and 128 to outer edges of the gas diffusion layers 133 and 134 are located in the region 2.
  • gaskets 153 and 154 are located for sealing so that a fuel gas and an oxidant gas will not leak to outside, so that the gas channels 147 and 148 are sealed against outside.
  • the sizes of the catalyst layers 127 and 128 are usually different in some degree by the process. Accordingly, in fact, misalignment in some degree may occur also at end edges of the catalyst layers 127 and 128 shown in Fig. 11 .
  • misalignment in some degree may similarly occur also at end edges of the gas diffusion layers 133 and 134 which cover such catalyst layers 127 and 128.
  • the catalyst layer end edge 130 between the end edge of the catalyst layer 127 and the end edge of the catalyst layer 128, one which is closer to the region 1 is defined as the catalyst layer end edge 130 (in the case of Fig. 11 , the end edge of the catalyst layer 128 is closer to the region 1 than the end edge of the catalyst layer 127, and therefore, the end edge of the catalyst layer 128 is defined as the catalyst layer end edge 130).
  • the end edge of the gas diffusion layer 133 and the end edge of the gas diffusion layer 134 one which is farther to the region 1 is defined as the gas diffusion layer end edge 140 (in the case of Fig. 11 , the end edge of the gas diffusion layer 133 is farther from the region 1 than the end edge of the gas diffusion layer 134, and therefore, the end edge of the gas diffusion layer 133 is defined as the gas diffusion layer end edge 140).
  • the region from the catalyst layer end edge 130 to the gas diffusion layer end edge 140 is disposed so as to be located in the region 2 having a non-perforated sheet disposed, so that the increase of gas leakage is suppressed even when the pressure is strongly exerted on the gas diffusion end edge 140 during bonding of the gas diffusion layer or even when the polymer electrolyte membrane 111 is partly damaged by creeping during the operation, whereby it is possible to prevent deterioration of the polymer electrolyte membrane 111 or short circuiting of the electrodes due to e.g. a local burning reaction.
  • the polymer electrolyte membrane-electrode assembly 137 for fuel cells having a long life.
  • Fig. 12 shows a single cell for fuel cells as the second embodiment of the present invention.
  • the perforated sheet 213 of a single cell 400 has the region 3 having a plurality of through-holes 117 formed on a farther outer peripheral portion of the region 2.
  • a plan view illustrating the perforated sheet 213 is the same as in Fig. 7
  • a view taken in the direction of B-B arrow in Fig. 12 is the same as in Fig. 8 respectively. Therefore, such views are omitted.
  • the region 3 allows the ion exchange resins on both surfaces to be connected through the through-holes 117 of the perforated sheet 213 also at the peripheral portion of the membrane, whereby it is possible to prevent peeling of the perforated sheet 213 and the ion exchange resins.
  • the region from the catalyst layer end edge 130 to the gas diffusion layer end edge 140 is located at a center portion in the width of the region 2.
  • such a width of the region 2 is preferably from about 2 to 24 mm, more preferably from about 3 to 12 mm, further preferably from about 4 to 8 mm.
  • the average area per through-hole 117 gradually becomes small towards the region 2 as shown in Fig. 9 .
  • the open area ratio gradually, it is possible to prevent concentration of the stress at the boundary between the region 1 and the region 2 and the boundary between the region 2 and the region 3.
  • the number of the through-holes 117 may gradually be decreased as shown in Fig. 10 .
  • Fig. 13 shows the second mode (cross-sectional view) of a single cell for fuel cells as the second embodiment of the present invention.
  • the region 1 and the region 3 of a polymer electrolyte membrane 311 constituting a single cell 500 are not reinforced by a reinforcement.
  • Only the region 2 is reinforced by a reinforcement 313 made of a non-perforated sheet in the form of a frame. Therefore, the region 1 and the region 3 may be made to be a polymer electrolyte membrane having high proton conductivity.
  • a membrane-catalyst layer assembly 331 is constituted by the polymer electrolyte membrane 311 and the catalyst layers 127 and 128, and, on both outer surfaces of the membrane-catalyst layer assembly 331 on the side of the catalyst layers 127 and 128, the gas diffusion layers 133 and 134 are respectively disposed.
  • a membrane-electrode assembly 337 is constituted by the membrane-catalyst layer assembly 331 and the gas diffusion layers 133 and 134, and, on both outer surfaces of the membrane-electrode assembly 337 on the side of the gas diffusion layers 133 and 134, gas channels 147 and 148 are formed between them and the separators 141 and 142.
  • Fig. 14 shows a cross-sectional view illustrating a single cell for fuel cells as a basis for the third embodiment of the present invention.
  • a plan view illustrating the perforated sheet 113 is the same as in Fig. 2
  • a view taken in the direction of arrow A-A arrow in Fig. 14 is the same as in Fig. 3
  • a vertically cross-sectional view illustrating the polymer electrolyte membrane 111 is the same as in Fig. 4 respectively. Therefore, such views are omitted.
  • the gas diffusion layers 133 and 134 are disposed so as to cover not only the surfaces of the catalyst layers 127 and 128 but also their sides, and the gas diffusion layers 133 and 134 are in surface contact with the polymer electrolyte membrane 111 at the contact surfaces 133a. Further, such gas diffusion layers are disposed so that the region from outer edges of the catalyst layers 127 and 128 to outer edges of the gas diffusion layers 133 and 134 is located in the region 2. Although not shown in the drawings, the gas diffusion layers 133 and 134 may be disposed only on the catalyst layers 127 and 128 flatly so as not to cover their sides.
  • Inner peripheral portions of the gaskets 153 and 154 on the side of the catalyst layers 127 and 128 are disposed so as to be located in the region 2. It is desired that such inner peripheral portions 300 of the gaskets 153 and 154 are located at about the center of the region 2.
  • the inner peripheral portions 300 of the gaskets 153 and 154 are disposed so as to be located in the region 2 having no through-holes formed, so that the increase of gas leakage is suppressed even when the pressure is strongly exerted on the polymer electrolyte membrane 111 during bonding the gaskets or even when the polymer electrolyte membrane 111 is partly damaged by creeping during the operation, whereby it is possible to prevent deterioration of the polymer electrolyte membrane 111 or short circuiting of the electrode due to e.g. a local burning reaction.
  • the width of such a region 2 is preferably from about 2 to 24 mm, more preferably from about 3 to 12 mm, further preferably from about 4 to 8 mm.
  • Fig. 15 shows a single cell for fuel cells as the third embodiment of the present invention.
  • the perforated sheet 213 of a single cell 700 has a region 3 having a plurality of through-holes 117 formed at a farther outer peripheral portion of the region 2.
  • a plan view of the perforated sheet 213 is the same as in Fig. 7 and a view taken in the direction of arrow B-B in Fig. 15 is the same as in Fig. 3 respectively. Therefore, such views are omitted.
  • a polyphenylene sulfide film (tradename: Torelina 3030-12, manufactured by Toray Industries, Inc.) of a 200 mm square having a thickness of 12 ⁇ m, 213,280 through-holes having a diameter of 300 ⁇ m (average area per through-hole: about 0.071 mm 2 ) were formed in a staggered arrangement so as to have a center distance of 350 ⁇ m by multiple spindle drilling, to prepare a perforated sheet 113 having a region 1 of a 150 mm square having an open area ratio of about 67% and a region 2 having no apertures outside thereof.
  • a polyphenylene sulfide film (tradename: Torelina 3030-12, manufactured by Toray Industries, Inc.) of a 200 mm square having a thickness of 12 ⁇ m was immersed in hot water of 90°C for 16 hours, the film was taken out and water on the film surface was wiped out with a filter paper, whereupon the weight was measured. After the measurement, nitrogen was circulated at 25°C for 16 hours for drying, whereupon the dry weight was measured. The water content was found to be 0.2%. Here, the water content is a water content against the dry weight of the film, and the same applies hereinafter.
  • catalyst layers 127 and 128 are prepared as follows. First, the dispersion a and a supported - catalyst having a 55 mass% of platinum supported on carbon are dispersed in a dispersion medium having ethanol and water mixed (at a mass ratio of 1:1), and the catalyst dispersion having a solid content concentration of 14 mass% thus obtained is applied in a 154 mm square at the center portion on one side of a polymer electrolyte membrane 111 to form a catalyst layer 128 having platinum supported in an amount of about 0.4 mg/cm 2 , as a cathode.
  • the dispersion a and a supported catalyst having a 50 mass% of an alloy consisting of platinum and ruthenium, supported on carbon are dispersed in a dispersion medium having ethanol and water mixed (at a mass ratio of 1:1), and the catalyst dispersion having a solid content concentration of 14 mass% thus obtained is applied in a 154 mm square on the center portion on the other side of the polymer electrolyte membrane 111 to form a catalyst layer 127 having platinum supported in an amount of about 0.3 mg/cm 2 , as an anode, whereby a membrane-catalyst layer assembly 131 is prepared.
  • a gas diffusion layer of a 156 mm square having an electroconductive layer with a thickness of about 10 ⁇ m composed of carbon black and polytetrafluoroethylene particles formed on, a carbon cloth substrate with a thickness of about 300 ⁇ m is disposed at the center of each side of the membrane-catalyst layer assembly 131 so that such an electroconductive layer is in contact with the membrane-catalyst layer assembly 131.
  • this product is sandwiched between a pair of separators 141 and 142 having gas channels 147 and 148 for supply of reaction gases and between gaskets 153 and 154 for sealing made of fluorine rubber having an inside dimension of a 158 mm square; to obtain a single cell 100 (300, 600) for fuel cells, having an effective electrode area of 225 cm 2 .
  • the cell temperature of such a single cell 100 (300, 600) is controlled to be 90°C, and hydrogen gas is supplied to the anode side and air is supplied to the cathode side, respectively.
  • the gases are supplied to the fuel cell after humidified so as to have a dew point of 70°C respectively and so that the utilization rate of hydrogen gas will be 80% and the utilization rate of air will be 50%.
  • Fig. 16 shows the relation between the elapsed time and the cell voltage when a continuous operation is carried out at a cell temperature of 90°C and at a current density of 0.15 A/cm 2 .
  • a polyphenylene sulfide film (tradename: Torelina 3030-12, manufactured by Toray Industries, Inc.) of a 200 mm square having a thickness of 12 ⁇ m
  • 213,280 through-holes 117 having a diameter of 300 ⁇ m are formed in a staggered arrangement so as to have a center distance of 350 ⁇ m by multiple spindle drilling to prepare the region 1 of a 150 mm square with an open area ratio of about 67%
  • through-holes 117 having a diameter of 300 ⁇ m are formed in a staggered arrangement so as to have a center distance of 350 ⁇ m by multiple spindle drilling, to prepare the region 3 with an open area ratio of about 67%, whereby a perforated sheet 213 is prepared in which the region 2 with no apertures has a width of 7 mm.
  • a cathode and an anode are formed on such a polymer electrolyte membrane 211, and its contour is punched by a Thomson die to obtain a membrane-catalyst layer assembly 231 (corresponding to the membrane-catalyst layer assembly 131 shown in Fig.1 ) having a contour of a 165 mm square.
  • gas diffusion layers 133 and 134 are disposed on such a membrane-catalyst layer assembly 231 to obtain a single cell 200 (400, 700) for fuel cells, having an effective electrode area of 225 cm 2 .
  • the cell temperature of such a single cell 200 (400, 700) is controlled to be 90°C, and hydrogen gas is supplied to the anode side and air is supplied to the cathode side, respectively.
  • gases are supplied to the fuel cell after humidified so as to have a dew point of 70°C respectively and so that the utilization rate of hydrogen gas will be 80% and the utilization rate of air will be 50%.
  • Fig. 16 shows the relation between the elapsed time and the cell voltage when a continuous operation is carried out at a cell temperature of 90°C and at a current density of 0.15 A/cm 2 .
  • a cathode and an anode are formed on the polymer electrolyte membrane 211, and its contour is punched by a Thomson die to obtain a membrane-catalyst layer assembly 231 having a contour of a 165 mm square.
  • gas diffusion layers 133 and 134 are disposed on such a membrane-catalyst layer assembly 231 to obtain a single cell 200 (400, 700) for fuel cells, having an effective electrode area of 225 cm 2 .
  • the cell temperature of such a single cell 200 (400, 700) is controlled to be 90°C, and hydrogen gas is supplied to the anode side and air is supplied to the cathode side, respectively.
  • gases are supplied to the fuel cell after humidified so as to have a dew point of 70°C respectively and so that the utilization rate of hydrogen gas will be 80% and a utilization rate of air will be 50%.
  • Fig. 16 shows the relation between the elapsed time and the cell voltage when a continuous operation is carried out at a cell temperature of 90°C and at a current density of 0.15 A/cm 2 .
  • a cathode and an anode are formed on the membrane M1, and its contour is punched by a Thomson die to obtain a membrane-catalyst layer assembly CCM1 having a contour of a 165 mm square.
  • gas diffusion layers 133 and 134 are disposed on such a membrane-catalyst layer assembly CCM1 to obtain a single cell for fuel cells, having an effective electrode area of 225 cm 2 .
  • the cell temperature of such a single cell is controlled to be 90°C, and hydrogen gas is supplied to the anode side and air is supplied to the cathode side, respectively.
  • gases are supplied to the fuel cell after humidified so as to have a dew point of 70°C respectively and so that the utilization rate of hydrogen gas will be 80% and the utilization rate of air will be 50%.
  • Fig. 16 shows the relation between the elapsed time and the cell voltage, when a continuous operation is carried out at a cell temperature of 90°C and at a current density of 0.15 A/cm 2 .
  • a polyphenylene sulfide film (tradename: Torelina 3030-12, manufactured by Toray Industries, Inc.) of a 200 mm square having a thickness of 12 ⁇ m, 275,232 through-holes 117 having a diameter of 300 ⁇ m (average area per through-hole: about 0.071 mm 2 ) are formed in a staggered arrangement so as to have a center distance of 350 ⁇ m by multiple spindle drilling, to prepare a perforated sheet having an open area ratio of about 67% and having a region of a 170 mm square.
  • a polyphenylene sulfide film (tradename: Torelina 3030-12, manufactured by Toray Industries, Inc.) of a 200 mm square having a thickness of 12 ⁇ m
  • 275,232 through-holes 117 having a diameter of 300 ⁇ m (average area per through-hole: about 0.071 mm 2 ) are formed in a staggered arrangement so as to have a center distance of 350 ⁇
  • Example 2 a cathode and an anode were formed on such a polymer electrolyte membrane, and its contour was punched by a Thomson die to obtain a membrane-catalyst layer assembly CCM2 having a contour of a 165 mm square.
  • gas diffusion layers 133 and 134 were disposed on such a membrane-catalyst layer assembly CCM2 to obtain a single cell for fuel cells, having an effective electrode area of 225 cm 2 .
  • the cell temperature of such a single cell is controlled to be 90°C, and hydrogen gas is supplied to the anode side and air is supplied to the cathode side, respectively.
  • gases are supplied to the fuel cell after humidified so as to have a dew point of 70°C respectively and so that the utilization rate of hydrogen gas will be 80% and the utilization rate of air will be 50%.
  • Fig. 16 shows the relation between the elapsed time and the cell voltage when a continuous operation is carried out at a cell temperature of 90°C and at a current density of 0.15 A/ cm2 .
  • the perforated sheet is in such a state that only the region 1 is formed alone and no region 2 is formed thereon, whereby the cell voltage abruptly decreases at about a time when the elapsed time is beyond 1,200 hours as shown in Fig.16 .

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Abstract

L’invention porte sur un ensemble d’électrode à membrane pour pile à combustible polymère solide d’une excellente stabilité dimensionnelle et d’une excellente résistance mécanique avec une durabilité appréciable pendant la production d’énergie. L’invention concerne également une pile à combustible polymère solide. Spécifiquement, une membrane électrolytique polymère solide (111, 211, 311) comprend une région 1 possédant une conductivité protonique dans toute l’épaisseur de la membrane et une région 2 entourant la région 1 et sans conductivité protonique dans l’épaisseur de la membrane du fait d’une feuille non perforée disposée dans celle-ci. Des couches catalytiques (127, 128) sont disposées pour que les périphéries externes soient comprises dans la région 2.

Claims (11)

  1. Assemblage de membrane-électrode (137, 237, 337) pour des piles à combustible à électrolyte polymère, qui comprend une membrane d'électrolyte polymère (111, 211, 311) et des électrodes comprenant des couches de catalyseur (127, 128) contenant un catalyseur, disposées sur les deux côtés de la membrane d'électrolyte polymère (111, 211, 311), et des couches de diffusion de gaz (133, 134) supportant les couches de catalyseur (127, 128) à l'intérieur de leurs portions périphériques, caractérisé en ce que la membrane d'électrolyte polymère (111, 211, 311) a une première région (121, 1) présentant une conductivité des protons sur la totalité de la membrane dans le sens de l'épaisseur et une deuxième région (2) située au niveau de la portion périphérique extérieure de la première région (121, 1) et ayant une feuille non perforée disposée de façon que la deuxième région (2) ne présente pas de conductivité des protons sur la totalité de la membrane dans le sens de l'épaisseur, et des bords extérieurs des couches de catalyseur (127, 128) sont disposés de façon à être situés dans la deuxième région (2), dans lequel une ligne de séparation (118) pour séparer la première région (121, 1) et la deuxième région (2) est définie virtuellement, et la distance entre la ligne de séparation (118) et le bord d'extrémité de couche de catalyseur (130) est de 1 à 12 mm, dans lequel la membrane d'électrolyte polymère (111, 211, 311) a une troisième région (3) présentant une conductivité des protons dans une autre portion périphérique extérieure de la deuxième région (2) ; et dans lequel la membrane d'électrolyte polymère (111, 211, 311) a une couche de garnissage (114) comprenant au moins un matériau de renforcement choisi dans l'ensemble constitué par un matériau de renforcement fibreux, un matériau de renforcement fibrillé, une membrane poreuse, une étoffe tissée, une étoffe non tissée et une feuille perforée (113, 213) ayant une pluralité de trous traversants (117) formés, et une résine échangeuse d'ions tassée dans des parties de vide du matériau de renforcement ; dans la première région (121, 1), le matériau de renforcement a des portions de vide et présente une conductivité des protons à travers les portions de vide ; et dans la deuxième région (2), le matériau de renforcement n'a pas de portions de vide.
  2. Assemblage de membrane-électrode (137, 237, 337) selon la revendication 1, dans lequel des régions entières allant des bords extérieurs des couches de catalyseur (127, 128) aux bords extérieurs des couches de diffusion de gaz (133, 134) sont situées dans la deuxième région (2).
  3. Assemblage de membrane-électrode (137, 237, 337) selon la revendication 1 ou 2, dans lequel les portions périphériques extérieures des couches de diffusion de gaz (133, 134) sont disposées à l'intérieur de la portion périphérique de la membrane d'électrolyte polymère (111, 211, 311) ; sur les deux côtés de la membrane d'électrolyte polymère (111, 211, 311), des joints d'étanchéité (153, 154) ayant des portions périphériques intérieures localisées à l'extérieur des portions périphériques extérieures des électrodes sont disposés de façon à prendre en sandwich la membrane d'électrolyte polymère (111, 211, 311) ; et les portions périphériques intérieures des joints d'étanchéité (153, 154) sont disposées de façon à être en contact avec la membrane d'électrolyte polymère (111, 211, 311), dans la deuxième région (2).
  4. Assemblage de membrane-électrode (137, 237, 337) selon l'une quelconque des revendications 1 à 3, dans lequel la membrane d'électrolyte polymère (111, 211, 311) a la couche de garnissage (114) et une couche de résine (125) faite uniquement d'une résine échangeuse d'ions formée sur au moins un côté de la couche de garnissage (114).
  5. Assemblage de membrane-électrode (137, 237, 337) selon l'une quelconque des revendications 1 à 4, dans lequel le matériau de renforcement est fait en une feuille perforée (113, 213) ayant une pluralité de trous traversants (117) formés dans la première région (121, 1) et n'ayant pas de trous traversants formés dans la deuxième région (2).
  6. Assemblage de membrane-électrode (137, 237, 337) selon la revendication 5, dans lequel les trous traversants (117) ont une surface moyenne par trou traversant de 1 x 10-3 à 20 mm2 et sont formés pratiquement parallèles au sens de l'épaisseur de la feuille perforée (113, 213), et la première région (121, 1) dans la feuille perforée (113, 213) a une proportion de zones ouvertes de 30 à 80 %, par les trous traversants (117).
  7. Assemblage de membrane-électrode (137, 237, 337) selon la revendication 5 ou 6, dans lequel la membrane d'électrolyte polymère (111, 211, 311) a la troisième région (3) présentant une conductivité des protons au niveau de portions périphériques plus extérieures de la deuxième région (2) ; la feuille perforée (113, 213) a une pluralité de trous traversants (117) dans la troisième région (3), et la membrane d'électrolyte polymère (111, 211, 311) présente une conductivité des protons dans le sens de l'épaisseur à travers les trous traversants (117).
  8. Assemblage de membrane-électrode (137, 237, 337) selon l'une quelconque des revendications 5 à 7, dans lequel, dans au moins l'une des portions de frontière où les régions respectives sont en contact, la surface moyenne, par trou traversant, des trous traversants, devient progressivement petite, ou bien le nombre de trous traversants par unité de surface diminue progressivement en direction de la deuxième région.
  9. Assemblage de membrane-électrode (137, 237, 337) selon l'une quelconque des revendications 1 à 8, dans lequel la feuille perforée (113, 213) est faite d'un matériau ayant une teneur en eau d'au plus 5 % après achèvement d'une immersion dans de l'eau chaude à 90°C pendant 16 heures, élimination de l'eau sur la surface, mesure du poids, séchage à 25°C pendant 16 heures via circulation d'azote, et mesure du poids sec, dans lequel la teneur en eau est une teneur en eau par rapport au poids à sec du matériau.
  10. Assemblage de membrane-électrode (137, 237, 337) selon l'une quelconque des revendications 1 à 9, dans lequel le matériau (matériau constitutif) de la feuille perforée (113, 213) est au moins un membre choisi dans l'ensemble constitué par un polytétrafluoroéthylène, un copolymère de tétrafluoroéthylène/hexafluoropropylène, un copolymère de tétrafluoroéthylène/perfluoroalcoxyéthylène, un copolymère de tétrafluoroéthylène/éthylène, un polyéthylène, un polypropylène, un polyéther-amide, un polyéther-imide, une polyéther-cétone, une polyéther-éthercétone, une polysulfone, une polyéthersulfone, un poly(sulfure de phénylène), un poly(oxyde de phénylène), un polyphosphazène, un polyarylate, un polyimide, un polyamide-imide et un polybenzimidazole.
  11. Pile à combustible à électrolyte polymère, qui comprend des piles stratifiées (100, 200, 300, 400, 500, 600, 700), ayant chacune des séparateurs (141, 142) disposés sur les deux côtés de l'assemblage de membrane-électrode (137, 237, 337) tel que défini dans l'une quelconque des revendications 1 à 10.
EP05775096A 2004-08-30 2005-08-29 Ensemble d'électrode à membrane pour pile à combustible polymère solide et pile à combustible polymère solide Expired - Fee Related EP1798794B1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018130467A1 (de) 2018-11-30 2020-06-04 Schuler Pressen Gmbh Verfahren zur Herstellung eines Brennstoffzellenstapels

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100511794C (zh) 2004-08-30 2009-07-08 旭硝子株式会社 固体高分子型燃料电池用膜电极接合体及固体高分子型燃料电池
US20080261095A1 (en) * 2005-06-20 2008-10-23 Masaki Yamauchi Membrane-Electrode Assembly, Method for Manufacturing the Same, and Fuel Cell
US7879029B2 (en) * 2005-12-30 2011-02-01 Biosense Webster, Inc. System and method for selectively energizing catheter electrodes
JP2007250339A (ja) * 2006-03-15 2007-09-27 Toshiba Corp 燃料電池
KR100711897B1 (ko) * 2006-05-17 2007-04-25 삼성에스디아이 주식회사 물회수 및 순환구조를 갖는 연료전지 시스템
CN101118972B (zh) * 2006-08-04 2010-06-16 上海清能燃料电池技术有限公司 一种燃料电池的密封结构
US8431285B2 (en) * 2006-11-03 2013-04-30 GM Global Technology Operations LLC Edge design for ePTFE-reinforced membranes for PEM fuel cells
WO2008056661A1 (fr) * 2006-11-07 2008-05-15 Panasonic Corporation Film double de renfort, couche de catalyseur de film, film électrode, et pile à combustible à électrolyte de polymérique
WO2008090778A1 (fr) * 2007-01-22 2008-07-31 Panasonic Corporation Corps lié d'élément de renforcement film-film, corps lié de couche film-catalyseur, corps lié film-électrode, et pile à combustible de type polyélectrolyte
JP5214471B2 (ja) * 2007-01-29 2013-06-19 パナソニック株式会社 膜−膜補強部材接合体、膜−触媒層接合体、膜−電極接合体、及び高分子電解質形燃料電池
US7597617B2 (en) * 2007-03-02 2009-10-06 Andrew Solberg Gas diffusion device
CN101632192B (zh) * 2007-03-14 2012-05-02 松下电器产业株式会社 膜-膜增强部件组件、膜-催化剂层组件、膜-电极组件、高分子电解质型燃料电池、以及膜-电极组件的制造方法
US20100068592A1 (en) * 2007-08-09 2010-03-18 Matsushita Electric Industrial Co., Ltd. Electrodes for use in hydrocarbon-based membrane electrode assemblies of direct oxidation fuel cells
JP2009193860A (ja) * 2008-02-15 2009-08-27 Asahi Glass Co Ltd 固体高分子形燃料電池用膜電極接合体およびその製造方法
US8366884B2 (en) * 2008-04-30 2013-02-05 Alcatel Lucent Plating apparatus with direct electrolyte distribution system
JP2010027461A (ja) * 2008-07-22 2010-02-04 Toyota Motor Corp 膜電極接合体とその製造方法およびそれを用いた固体高分子形燃料電池
JP5172792B2 (ja) * 2009-07-31 2013-03-27 本田技研工業株式会社 固体高分子型燃料電池用膜−電極構造体及び固体高分子型燃料電池
CA2779049C (fr) * 2009-10-26 2014-11-25 Asahi Kasei Chemicals Corporation Membrane echangeuse de cations, cellule electrolytique l'utilisant et procede de fabrication d'une membrane echangeuse de cations
JP5883301B2 (ja) * 2011-02-07 2016-03-15 日本バイリーン株式会社 水分管理シート、ガス拡散シート、膜−電極接合体及び固体高分子形燃料電池
DE102011106767B3 (de) * 2011-06-01 2012-01-12 Daimler Ag Elektrolytmembrananordnung für eine Brennstoffzelle und Verfahren zu deren Herstellung
US10074866B2 (en) 2012-07-02 2018-09-11 Panasonic Intellectual Property Management Co., Ltd. Membrane electrode assembly for polymer electrolyte fuel cell, method of producing the same and polymer electrolyte fuel cell
CA2878834C (fr) 2012-07-10 2016-01-05 Nissan Motor Co., Ltd. Ensemble electrode a membrane
ES2629177T3 (es) * 2012-07-10 2017-08-07 Areva Stockage D'energie Pila de combustible con aislamiento eléctrico mejorado
US9728802B2 (en) 2013-05-14 2017-08-08 Giner, Inc. Micromold methods for fabricating perforated substrates and for preparing solid polymer electrolyte composite membranes
GB201420934D0 (en) * 2014-11-25 2015-01-07 Johnson Matthey Fuel Cells Ltd Membrane-seal assembly
CN110114926B (zh) * 2016-12-28 2022-04-15 本田技研工业株式会社 燃料电池的制造方法及加工装置
CN109473707B (zh) * 2017-09-08 2022-05-31 徐煜 质子交换膜燃料电池的质子交换膜
NL2022069B1 (en) * 2018-11-23 2020-06-05 Hyet Holding B V Solid-state compressor

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU664703B2 (en) 1991-06-04 1995-11-30 Ballard Power Systems Inc. Gasketed membrane electrode assembly for electrochemical fuel cells
JP3368907B2 (ja) * 1991-07-17 2003-01-20 富士電機株式会社 固体高分子電解質型燃料電池のシ−ル構造
JP2961161B2 (ja) 1991-12-21 1999-10-12 工業技術院長 高分子電解質型燃料電池の製造法
US5264299A (en) * 1991-12-26 1993-11-23 International Fuel Cells Corporation Proton exchange membrane fuel cell support plate and an assembly including the same
JP3052536B2 (ja) * 1992-02-26 2000-06-12 富士電機株式会社 固体高分子電解質型燃料電池
JPH07220742A (ja) 1994-01-27 1995-08-18 Matsushita Electric Ind Co Ltd 固体高分子電解質型燃料電池及び該燃料電池の電極−イオン交換膜接合体の製造方法
JPH08185872A (ja) * 1994-12-28 1996-07-16 Tokyo Gas Co Ltd 固体高分子型燃料電池及びその製造方法
JPH08259710A (ja) * 1995-03-28 1996-10-08 Sumitomo Electric Ind Ltd イオン交換膜
JPH09289028A (ja) 1996-04-24 1997-11-04 Tanaka Kikinzoku Kogyo Kk 固体高分子電解質型燃料電池用電解質膜、ガスシール構造及びスタック
JP3805495B2 (ja) 1996-09-24 2006-08-02 松下電器産業株式会社 固体高分子型燃料電池
JP3810178B2 (ja) 1997-05-06 2006-08-16 松下電器産業株式会社 高分子電解質型燃料電池の製造方法
JPH11204122A (ja) 1998-01-19 1999-07-30 Toshiba Corp 固体高分子電解質型燃料電池
JP2000215903A (ja) * 1999-01-25 2000-08-04 Toshiba Corp 固体高分子電解質型燃料電池
JP2000260443A (ja) * 1999-03-04 2000-09-22 Asahi Glass Co Ltd 固体高分子電解質型燃料電池
AU6060601A (en) * 2000-11-21 2002-06-03 Nok Corp Constituent part for fuel cell
US7217471B2 (en) * 2002-05-17 2007-05-15 3M Innovative Properties Company Membrane electrode assembly with compression control gasket
WO2004093228A1 (fr) * 2003-04-17 2004-10-28 Asahi Glass Company, Limited Membrane electrolyte de polymere solide, electrode membranaire pour pile a combustible a polymere solide, et procede de production de membranes electrolytes de polymere solide
JP2005216769A (ja) * 2004-01-30 2005-08-11 Asahi Glass Co Ltd 固体高分子電解質膜、その製造方法、及び固体高分子電解質膜を有する膜電極接合体
JP2005302526A (ja) * 2004-04-12 2005-10-27 Asahi Glass Co Ltd 固体高分子電解質膜及び固体高分子電解質膜を有する膜電極接合体
US7378176B2 (en) * 2004-05-04 2008-05-27 Angstrom Power Inc. Membranes and electrochemical cells incorporating such membranes
US20060029850A1 (en) * 2004-08-03 2006-02-09 Peter Szrama Fuel cell assembly with structural film
CN100511794C (zh) 2004-08-30 2009-07-08 旭硝子株式会社 固体高分子型燃料电池用膜电极接合体及固体高分子型燃料电池
ATE431374T1 (de) 2004-12-22 2009-05-15 Asahi Glass Co Ltd Elektrolytmembran, verfahren zu deren herstellung und membran-elektrodenanordnung für festpolymerbrennstoffzellen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018130467A1 (de) 2018-11-30 2020-06-04 Schuler Pressen Gmbh Verfahren zur Herstellung eines Brennstoffzellenstapels

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CN100511794C (zh) 2009-07-08
KR20070046092A (ko) 2007-05-02
US7521144B2 (en) 2009-04-21
EP1798794A1 (fr) 2007-06-20
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